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Fuel
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Institute of Chemical Technology, Prague Department of Petroleum Technology and Alternative Fuels, Technick 5, 166 28 Prague 6, Czech Republic
Research Institute of Inorganic Chemistry, Department of Rening and Petrochemical Research, 436 70 Litvnov Zluz 1, Czech Republic
a r t i c l e
i n f o
Article history:
Received 2 March 2009
Received in revised form 16 September
2009
Accepted 17 September 2009
Available online 1 October 2009
Keywords:
Hydroprocessing
Rapeseed oil
Biodiesel
Hydrodeoxygenation
a b s t r a c t
This paper deals with the hydroprocessing of rapeseed oil as a source of hydrocarbon-based biodiesel.
Rapeseed oil was hydroprocessed in a laboratory ow reactor under four combinations of reaction conditions at temperatures 310 and 360 C and under hydrogen pressure of 7 and 15 MPa. A commercial
hydrotreating NiMo/alumina catalyst was used. Reaction products contained mostly n-heptadecane
and n-octadecane accompanied by low concentrations of other n-alkanes and i-alkanes. Reaction product
obtained at 360 C and 7 MPa was blended into mineral diesel fuel in several concentration levels ranging
from 5 to 30 wt.%. It was found, that most of the standard parameters were similar to or better than those
of pure mineral diesel. On the other hand, low-temperature properties were worse, even after addition of
high concentrations of ow improvers.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Hydroprocessing of vegetable oils allows easy transformation of
fatty acid triglycerides into hydrocarbons. Three most important
reactions take place during hydroprocessing of vegetable oil [1]:
(i) Hydrogenation of double bonds present in unsaturated
chains of bonded fatty acids.
(ii) Hydrodeoxygenation (HDO), which results in removal of
oxygen atoms from carboxylic group in the form of water.
(iii) Hydrodecarboxylation (HDC), which leads to elimination of
carboxylic group in the form of carbon dioxide.
It was found that hydrogenation of double bonds precedes HDO
and HDC reactions [1]. HDO and HDC of saturated triglycerides
proceed at different reaction rates, which depend on reaction conditions and type of catalyst used. The changes in the respective
reaction rates can be observed by the changing ratio of the principal products, i.e. n-octadecane in the case of HDO and n-heptadecane in the case of HDC. In general, the main reaction products of
vegetable oil hydroprocessing are thus n-alkanes having the same
carbon atom number as fatty acids present in the original vegetable oil (HDO) and n-alkanes with the carbon atom number lower
by one as compared to the carbon atom number of fatty acids in
the original vegetable oil (HDC). Hydroprocessing of common veg-
* Corresponding author. Tel.: +420 220 444 236; fax: +420 220 444 321.
E-mail addresses: pavel.simacek@vscht.cz (P. imcek), david.kubicka@
vuanch.cz (D. Kubicka).
1
Tel.: +420 476 163 735; fax: +420 476 768 476.
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.09.017
612
2. Experimental
2.1. Hydroprocessing
Hydroprocessing of rapeseed oil was performed in a bench scale
ow reactor equipped with a salt bath heating system. The experimental set-up is schematically depicted in Fig. 1. All the feed and
product lines were heated to prevent feed and product solidication in the lines. The liquid products were stripped with hydrogen
FIRC
PIC
High-pressure
gas line H2
TIRC
TIR1-3
FIR
Off-gas
collection system
WIR
1 - analytical scales
2 - heated feed container
PIRC
3 - fixed-bed reactor
Liquid product
collection
613
400
350
Hydroprocessing of rapeseed oil yielded water, gaseous hydrocarbons and organic liquid product (OLP). The conversion of rapeseed oil was >99% at 310 C and complete conversion was achieved
at 360 C. The yields of the main products were as follows: OLP
83 wt.%, water 11 wt.% and gaseous hydrocarbons 6 wt.%. Beside
hydrogen, the reaction gas contained mainly propane (0.8
2.5 vol.%) and small amounts of carbon dioxide (0.050.3 vol.%),
carbon monoxide (up to 0.5 vol.%) and methane.
All OLPs were colourless or slightly yellowish liquids with density around 770 kg m 3 at 40 C. However, in the temperature
range of 2030 C they became solids. The composition of OLPs is
presented in Table 1. It is evident, that OLP is a mixture of saturated, in particular non-branched, hydrocarbons. Two hydrocarbons n-heptadecane and n-octadecane represent more than
75 wt.% of OLP in all cases. Besides other n-alkanes, the OLPs contained also i-alkanes and smaller amounts of cycloalkanes. Formation of i-alkanes was observed to increase with increasing reaction
temperature and pressure. Aromatics were found in OLPs only in
trace amounts (<0.1 wt.%) in some cases. The OLPs obtained at
310 C contained small amounts (up to 2 wt.%) of reaction intermediates (mainly stearic acid) and reactants. Traces of n-octadecanol,
another reaction intermediate, was also observed, but only in one
of the products. On contrary, the OLPs obtained at 360 C contained
no oxygenated compounds and they can be, thus, denoted as oxygen-free hydrocarbon mixtures.
300
310 C, 7 Mpa
310 C, 15 MPa
360 C, 7 MPa
360 C, 15 MPa
250
200
0
20
40
60
Recovery (vol.%)
80
100
Products obtained at 310 C showed increased acid number, probably due to carboxylic acid content (see Table 1 and 2).
The main disadvantage of OLPs as a potential component of diesel fuel consists in their poor low-temperature properties. All lowtemperature parameters (cloud point, pour point and cold lter
plugging point) fell into the range of +20 to +30 C (Table 2). Utilization of such a kind of diesel fuel in the pure form would be very
problematic even in countries with hot climate.
3.3. Mixed diesel fuels
Table 1
Composition (wt.%) of organic liquid products obtained under various reaction
conditions (temperature and pressure).
Component
n-alkanes 6 n-C16
n-heptadecane
n-octadecane
n-alkanes > n-C18
Other hydrocarbonsa
Palmitic acid (C16:0)
Stearic acid (C18:0)
n-octadecanol
Monoglycerides
Diglycerides
Triglycerides
Reaction conditions
310 C,
7 MPa
310 C,
15 MPa
360 C,
7 MPa
360 C,
15 MPa
5.0
18.4
70.6
3.3
1.1
0.6
0.1
0.1
0.8
4.9
10.5
78.2
3.2
2.3
0.6
0.1
0.1
0.1
5.8
24.9
58.1
4.5
6.7
6.3
24.9
51.8
3.6
13.4
a
This group includes all hydrocarbons except n-alkanes (contains more than 90%
i-alkanes C16C18).
Table 2
Physiochemical properties of organic liquid products obtained under various reaction
conditions.
Parameter
Reaction conditions
310 C,
7 MPa
772
Density at 40 C
(788b)
(kg m 3)a
4.15
Kin. viscosity at 40 C
(mm2 s 1)
Distillation
At 250 C recovered
<5
(vol.%)
At 350 C recovered
>95
(vol.%)
95 vol.% recovered at
339
(C)
Flash point in closed
>128
cup (C)
c
Cetane index
103
9
Sulfur (mg kg 1)
Nitrogen (mg kg 1)
11
95
Water (mg kg 1)
0.54
Acid number
(mg KOH g 1)
Low-temperature properties
Cloud point (C)
2628
CFPP (C)
>20
Pour point (C)
28
310 C,
15 MPa
360 C,
7 MPa
360 C,
15 MPa
771 (787b)
770 (786b)
4.11
771
(787b)
3.92
<5
<5
<5
>95
>95
>95
330
344
323
>128
125
120
105
9
11
95
0.65
103
10
11
66
0.06
103
10
11
42
0.05
2830
>20
29
2527
>20
25
2325
>20
23
3.82
a
Solid nature of the sample did not allow to measure its standard density at
15 C.
b
Approximate values (density at 15 C was calculated from density at 40 C
taking the sample as homogenous liquid).
c
Cetane index calculated with the estimated density at 15 C.
614
400
0%
5%
10%
20%
30%
-5
300
250
CFPP (C)
Temperature (C)
350
0%
10%
20%
30%
200
-10
-15
-20
-25
-30
150
0
20
40
60
80
100
-35
Recovery (vol.%)
100
200
300
400
500
Fig. 4. Cold lter plugging point (CFPP) of diesel fuels containing various amount of
organic liquid product (hydroprocessed rapeseed oil processed at 360 C and 7 MPa)
treated with ow improver Keroux 3566 (BASF).
5
0%
5%
10%
20%
30%
CFPP (C)
-5
-10
-15
-20
-25
-30
-35
0
100
200
300
400
500
Table 3
Physiochemical properties of mixed fuels containing various amount of organic liquid product (hydroprocessed rapeseed oil processed at 360 C and 7 MPa).
Parameter
Density at 15 C (kg m 3)
Kin. viscosity at 40 C (mm2 s
Distillation
At 250 C recovered (vol.%)
At 350 C recovered (vol.%)
95 vol.% recovered at (C)
Flash point in closed cup (C)
Cetane index
Sulfur (mg kg 1)
Nitrogen (mg kg 1)
Water (mg kg 1)
Low-temperature properties
Cloud point (C)
CFPP (C)
Pour point (C)
a
b
10
20
30
829
2.35
826
2.44
824
2.50
820
2.63
816
2.76
820845
2.004.50
48
95
351
72
52.1
10
37
40
45
95
350
72
54.3
10
36
41
42
95
352
73
56.7
10
34
43
36
95
350
74
60.6
10
32
45
27
95
352
76
65.7
10
29
48
<65
>85
<360
>55
>46
<10
<200
9
12
12
8
12
12
7
10
9
+3
3
3
< 8a
<(+5 to
Grade F diesel.
Maximum values for grades A, B, C, D, E and F is +5, 0,
5,
10,
15 and
20 C, respectively.
1
7
9
20)
4. Conclusions
Hydroprocessing of rapeseed oil at 360 C and 7 and 15 MPa
yielded oxygen-free hydrocarbon mixtures. Only trace amounts
of reactants and intermediates were observed in products obtained
at 310 C. The organic liquid products (OLPs) contained acyclic saturated hydrocarbons having carbon atom number ranging from
about 14 to 20, where n-alkanes C17 and C18 formed more than
75 wt.% of the product. The composition and physiochemical properties of hydroprocessed rapeseed oil predetermine this product as
a high cetane diesel fuel, but its poor low-temperature properties
(pour point higher than +20 C) prevents its utilization in the pure
form.
Mixed diesel fuels containing from 5 to 30 wt.% of OLP (obtained at 360 C and 7 MPa) met the European diesel fuel specication EN 590. The greatest benet of the mixed fuels is probably the
increase of the cetane index (by 214 units). On the other hand, the
ow improvers used were shown to be ineffective in lowering
CFPP. The mixed fuels thus met only diesel grade specications
B, C, D and E, respectively, while the basic mineral diesel treated
with ow improvers met F-grade specication (EN 590) easily.
615
Acknowledgement
This work was supported by the Ministry of Industry and Trade
of the Czech Republic (project FT-TA3/074) and by the Ministry of
Education, Youth and Sports of the Czech Republic (agreement No.
MSM 6046137304).
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